含Sn水滑石可见光催化降解对氯苯酚的研究

利用水滑石的优良结构特性, 将具有光催化活性的Sn引入水滑石中得到光催化性能较高的含Sn水滑石材料, 通过X射线粉末衍射(XRD)、傅里叶变换红外光谱(FTIR)、紫外可见漫反射图谱 (UV-Vis DRS)和比表面积测量(BET)技术对样品的晶相、分子结构、光学性能和比表面积进行分析表征。以可见光催化降解对氯苯酚(4-CP)为模型, 研究所合成样品的光催化活性。结果表明: 在可见光照射下, 水滑石骨架结构中含Sn的锌锡水滑石表现出更高的光催化活性, 对4-CP的降解率达到92.4%(去除量34.6 mg/g)。并利用气相色谱(GC)和密度泛函理论(DFT)对4-CP的降解中间产物和反应路径进行了推测, 发现光催化过程中的主要中间产物为对苯二酚和4-氯邻苯二酚。     

层状双氢氧化物改善地聚物抗氯离子渗透性能研究

本文提出利用经煅烧处理的层状双氢氧化物(LDHs)材料的阴离子交换与结构重建特性改善地聚物抗氯离子渗透性能。借助XRD与TEM分析表征了层状双氢氧化物经煅烧和氯离子插层后组成和结构的变化,采用电位滴定仪测试了NaCl溶液浸泡后地聚物样品距表面不同深度处的氯离子浓度演变规律,并通过SEM与MIP研究了煅烧处理的层状双氢氧化物对地聚物微结构的影响。结果表明:层状双氢氧化物经煅烧处理后在NaCl溶液中可通过吸附Cl-实现层状结构复原。煅烧处理的层状双氢氧化物可以提高地聚物的抗氯离子渗透性能,其3%的掺量可以减少地聚物氯离子渗透量44%,且有利于地聚物形成密实的浆体结构。     

固相剪切碾磨制备聚丙烯/层状双金属氢氧化物纳米复合材料的力学性能及热稳定性

采用湿法固相剪切碾磨法(S<'3>M)制备了部分剥离型聚丙烯(PP)/层状双金属氢氧化物(LDHs)纳米复合材料,研究了PP/LDHs纳米复合材料的力学性能和热稳定性.结果表明,相对于聚丙烯,固相剪切碾磨制备的PP/LDHs纳米复合材料可在拉伸强度保持不变的情况下,明显提高其断裂伸长率和冲击强度.如当LDHs质量分数为...     

Water‐Plasma‐Enabled Exfoliation of Ultrathin Layered Double Hydroxide Nanosheets with Multivacancies for Water Oxidation

An earth‐abundant and highly efficient electrocatalyst is essential for oxygen evolution reaction (OER) due to its poor kinetics. Layered double hydroxide (LDH)‐based nanomaterials are considered as promising electrocatalysts for OER. However, the stacking structure of LDHs limits the exposure of the active sites. Therefore, the exfoliation is necessary to expose more active sites. In addition, the defect engineering is proved to be an efficient strategy to enhance the performance of OER electrocatalysts. For the first time, this study prepares ultrathin CoFe LDHs nanosheets with multivacancies as OER electrocatalysts by water‐plasma‐enabled exfoliation. The water plasma can destroy the electrostatic interactions between the host metal layers and the interlayer cations, resulting in the fast exfoliation. On the other hand, the etching effect of plasma can simultaneously and effectively produce multivacancies in the as‐exfoliated ultrathin LDHs nanosheets. The increased active sites and the multivacancies significantly contribute to the enhanced electrocatalytic activity for OER. Compared to pristine CoFe LDHs, the as‐exfoliated ultrathin CoFe LDHs nanosheets exhibit excellent catalytic activity for OER with a ultralow overpotential of only 232 mV at 10 mA cm^?2 and possesses outstanding kinetics (the Tafel slope of 36 mV dec^?1). This work provides a novel strategy to exfoliate LDHs and to produce multivacancies simultaneously as highly efficient electrocatalysts for OER.     

纳米金催化剂Au/ZnAl-LDHs的制备及在CO常温氧化反应中的活性及稳定性

以人工合成的双羟基金属氢氧化物ZnAl-LDHs为载体,将预先制备的金溶胶通过静电吸附的方式负载到载体上,获得了纳米金催化剂Au/ZnAl-LDHs,用X射线粉末衍射(XRD)表征了催化剂的物相,用透射电镜(TEM)观察了纳米金颗粒的粒径分布,以CO的常温催化氧化为模型反应,分别考察了金溶胶制备过程中金前体HAuCl4·6H2O的浓度和还原剂THPC的用量、负载过程的pH值以及金的负载量等因素对金催化剂的活性和稳定性的影响。结果表明:在制备金溶胶的过程中,降低HAuCl4·6H2O的浓度并提高还原剂THPC的用量,可以制备出粒径分布处于1~7nm之间、平均粒径仅3.87nm的负载型纳米金颗粒,其对CO的常温转化率为100%,且其催化活性的稳定性明显提高;而在金溶胶的吸附负载过程中,使体系的pH值处于6~7的范围,有利于金溶胶在ZnAl-LDHs载体上的吸附负载,从而得到实际负载量更接近理论负载量的金催化剂样品,当金的实际负载量接近1%(质量分数)时,能够确保对CO的常温氧化转化率达到100%。     

Efficient Gene Therapy of Pancreatic Cancer via a Peptide Nucleic Acid (PNA)‐Loaded Layered Double Hydroxides (LDH) Nanoplatform

Pancreatic ductal adenocarcinoma (PDAC) is one of the deadliest malignant tumors with extremely poor prognosis due to the later stage diagnosis when surgical resection is no longer applicable. Alternatively, the traditional gene therapy which drives pancreatic cancer cells into an inactive state and inhibiting the proliferation and metastasis, presents potentials to safely inhibit pancreatic cancer progression, but unfortunately has received limited success to date. Here, an efficient gene therapy of pancreatic cancer is shown via a peptide nucleic acid (PNA)‐loaded layered double hydroxides (LDHs) nanoplatform. Compared with the traditional DNA‐ or RNA‐based gene therapies, the gene therapy using PNA features great advantages in recognizing and hybridizing with the target mutant sequences to form PNA–DNA hybrids with significantly enhanced stability due to the absence of electrostatic repulsion, and the constrained flexibility of the polyamide backbone. Moreover, ultrasmall LDHs are engineered to load PNA and the obtained PNA‐loaded LDH platform (LDHs/PNA) is capable of efficiently and selectively targeting the intranuclear mutant sequences thanks to the proton sponge effect. Treatments with LDHs/PNA demonstrate markedly inhibited growth of pancreatic cancer xenografts via a cancer cell proliferation suppression mechanism. The results demonstrate the great potentials of LDHs/PNA as a highly promising gene therapy agent for PDAC.     

焙烧Mg-Al水滑石水泥浆涂层对钢筋氯离子腐蚀的缓蚀性能

本工作研究了焙烧Mg-Al水滑石(LDO)水泥浆涂层对钢筋氯离子腐蚀的缓蚀性能。将焙烧Mg-Al水滑石材料添加到水泥浆中制备了复合水泥浆涂层,并涂覆在钢筋表面。由等温吸附实验、线性极化测试(LP)、电化学阻抗谱测试(EIS)研究了在混凝土模拟孔溶液中复合水泥浆涂层对钢筋氯离子腐蚀的缓蚀性能;此外,采用X射线衍射仪(XRD)和傅里叶变换红外光谱(FT-IR)检测了吸附实验前后水泥浆的物相变化,探讨了焙烧Mg-Al水滑石水泥浆涂层对钢筋氯离子腐蚀的缓蚀机理。结果表明,LDO的掺入能显著提高水泥浆体对氯离子的饱和吸附量,且随着LDO掺量的增加,复合水泥浆涂层的综合阻锈效果增强。复合LDO涂层缓释机理归因于层状结构的复原使其能有效地吸附氯离子并释放氢氧根离子,从而能有效阻止氯离子的侵蚀。     

Topotactically Transformed Polygonal Mesopores on Ternary Layered Double Hydroxides Exposing Under-Coordinated Metal Centers for Accelerated Water Dissociation

Layered double hydroxides (LDHs) have been recognized as potent electrocatalysts for oxygen evolution reaction (OER), but are lacking in hydrogen evolution reaction (HER) activities due to the sluggish kinetics of water dissociation in alkaline medium. Herein, aiming to simultaneously bolster the HER and OER kinetics, a metal–organic framework (MOF) mediated topotactic transformation tactic is deployed to fabricate holey ternary CoFeNi LDHs on nickel foam, exposing polygonal mesopores with atomistic edge steps and lattice defects. The optimized catalyst requires only an external voltage of 1.49 V to afford the water splitting current density of 10 mA cm⁻² apart from the superb electrolytic stability, far surpassing the benchmark Pt/C||RuO₂ couple. More importantly, mechanistic investigations utilizing advanced spectroscopies in conjunction with density function theory (DFT) understandings unravel while the synergetic effect among under-coordinated metal centers lowers the energy barrier of water dissociation, Fe-doping enables further modulating the d-band density of states (DOS) of Co and Ni in favor of intermediates binding, thereby promoting the intrinsic HER activity. Operando Raman studies reveal negligible structural change of the LDHs during the HER process, whereas for OER the active sites can quickly turn into oxyhydroxides in the presence of lattice defects and under-coordinated metal centers.     

Porous Hybrid Network of Graphene and Metal Oxide Nanosheets as Useful Matrix for Improving the Electrode Performance of Layered Double Hydroxides

Mesoporous hybrid network of reduced graphene oxide (rG‐O) and layered MnO₂ nanosheets could act as an efficient immobilization matrix for improving the electrochemical activity of layered double hydroxide (LDH). The control of MnO₂/rG‐O ratio is crucial in optimizing the porous structure and electrical conductivity of the resulting hybrid structure. The immobilization of Co‐Al‐LDH on hybrid MnO₂/rG‐O network is more effective in enhancing its electrode activity compared with that of on pure rG‐O network. The Co‐Al‐LDH?rG‐O?MnO₂ nanohybrid deliveres a greater specific capacitance than does MnO₂‐free Co‐Al‐LDH?rG‐O nanohybrid. The beneficial effect of MnO₂ incorporation on the electrode performance of nanohybrid is more prominent for higher current density and faster scan rate, underscoring the significant enhancement of the electron transport of Co‐Al‐LDH?rG‐O. This is supported by electrochemical impedance spectroscopy. The present study clearly demonstrates the usefulness of the porously assembled hybrid network of graphene and metal oxide nanosheets as an effective platform for exploring efficient LDH‐based functional materials.     

A High-Nickel Layered Double Hydroxides Cathode Boosting the Rate Capability for Chloride Ion Batteries with Ultralong Cycling Life

Chloride-ion batteries (CIBs) have drawn growing attention in large-scale energy storage applications owing to their comprehensive merits of high theoretical energy density, dendrite-free characteristic, and abundance of chloride-containing materials. Nonetheless, cathodes for CIBs are plagued by distinct volume effect and sluggish Cl⁻ diffusion kinetics, leading to inferior rate capability and short cycling life. Herein, an unconventional Ni₅Ti-Cl LDH is reported with a high nickel ratio as a cathode material for CIB. The reversible capacity of Ni₅Ti-Cl LDH retains 127.9 mAh g⁻¹ over 1000 cycles at a large current density of 1000 mA g⁻¹, which exceeds that of ever reported CIBs, with extraordinary low volume change of 1.006% during a whole charge/discharge process. Such superior Cl-storage performance is attributed to synergetic contributions consisting of high redox activity from Ni²⁺/Ni³⁺ and pinning Ti that restrains local structural distortion of LDH host layers and enhances adsorption intensity of chloride atoms during the reversible Cl⁻ intercalation/de-intercalation in LDH gallery, which are revealed by a comprehensive study including X-ray photoelectron spectroscopy, kinetic investigations, and DFT calculations. This work provides an effective strategy to design low-cost LDHs materials for high-performance CIBs, which are also applicable to other types of halide-ion batteries (e.g., fluoride-ion and bromide-ion batteries).     

微波场下纳米Mg-Al-LDHs及PO_4~(3-),P_2O_7~(4-)柱撑Mg-Al层状双氢氧化物的合成

用微波加热反应-变速滴加共沉淀法合成了[Mg-Al-CO3]纳米层状双氢氧化物,并以[Mg-Al-CO3]纳米层状双氢氧化物为前体,用微波加热反应-离子交换法制备了PO43-,P2O74-柱撑Mg-Al层状双氢氧化物。该法合成的[Mg-Al-CO3]纳米层状双氢氧化物的粒径约为10-40nm。讨论了微波和变速滴加碱液的速度对纳米层状双氢氧化物的合成的影响。用FT-IR、TEM与XRD对产物进行了表征,结果表明在微波加热反应的条件下可在短时间内用PO43-,P2O74-彻底交换CO32-。     

酒石酸柱撑水滑石吸附水中的Ni~(2+)的特性研究

采用离子交换法制得酒石酸插层MgAl水滑石(MgAl-TA LDHs),并进行了XRD、IR、SEM、比表面积及孔径分析表征。考察了MgAl-TA LDHs吸附剂对溶液中Ni 2+的吸附能力,探讨了水滑石吸附剂投加量、Ni 2+溶液浓度、pH值以及吸附温度对Ni 2+吸附率的影响,并进行了动力学和热力学特征的研究。结果表明,适宜的水滑石投加量为2g/L,pH值以中性为宜,对于Ni 2+浓度不超过100 mg/L的溶液室温下Ni 2+吸附率在60%以上,而高温有利于提高Ni 2+吸附率。吸附过程符合二级动力学模型,吸附等温曲线可用R-P模型来描述。吸附过程能够自发进行,为吸热过程,属于化学吸附。     

Cobalt–Nickel Layered Double Hydroxides Modified on TiO2 Nanotube Arrays for Highly Efficient and Stable PEC Water Splitting

TiO₂‐based photoanodes have attracted extensive attention worldwide for photoelectrochemical (PEC) water splitting, but these materials still suffer from poor electron–hole separation and low photoconversion efficiency. Here, the high PEC water splitting activity and long‐term stability against photocorrosion of well‐aligned hierarchical TiO₂@CoNi‐layered double hydroxides nanotube arrays (TiO₂@CoNi‐LDHs NTAs) are reported. The typical TiO₂@CoNi‐LDHs NTAs exhibits enhancing photocurrent density of 4.4 mA cm^?2 at a potential of 1.23 V (vs reversible hydrogen electrode) under AM 1.5G simulated sunlight (100 mW cm^?2), 3.3 times higher than that of the pristine TiO₂ sample. Moreover, this hierarchical electrode displays excellent stability against photocorrosion with initial activity loss no more than 1.0% even after 10 h irradiation in Na₂SO₄ electrolyte solution (pH 6.8), much competitive to those reported TiO₂‐based photoelectrodes. This work may offer a combinatorial synthesis strategy for the preparation of hierarchical architectures with high PEC performances.     

微波场下纳米Mg-Al-LDHs及PO43-,P2O74-柱撑Mg-Al层状双氢氧化物的合成

用微波加热反应-变速滴加共沉淀法合成了[Mg-Al-CO3]纳米层状双氢氧化物，并以[Mg-Al-CO3]纳米层状双氢氧化物为前体，用微波加热反应一离子交换法制备了PO4^3-，P2O7^4-柱撑Mg-Al层状双氢氧化物．该法合成的[Mg-Al-CO3]纳米层状双氢氧化物的粒径约为10～40nm．讨论了微波和变速滴加碱液的速度对纳米层状双氢氧化物的合成的影响．用FT-IR、TEM与XRD对产物进行了表征，结果表明在微波加热反应的条件下可在短时间内用PO4^3-,P2O7^4-彻底交换CO3^2-。